1. Field of the Invention
This invention relates to halogenated dioxolanes and dioxoles, their preparation and polymers of the dioxoles.
2. References
U.S. Pat. No. 2,925,424, issued to Simmons on Feb. 16, 1960, discloses cyclic fluoroketals of the formula ##STR1## prepared by reacting fluoroketones with .beta.-haloethanol; wherein R.sub.x and R.sub.y are perhalohydrocarbyl radicals of 1 to 7 carbon atoms, and R.sub.z is a divalent hydrocarbyl or halohydrocarbyl radical of 1 to 12 carbon atoms.
U.S. Pat. No. 3,308,107, issued to Selman, et al., on Mar. 7, 1967, discloses perfluoro-2-methylene-4-methyl-1,3-dioxolane, its preparation from perfluoro-2,4-dimethyl-2-fluoroformyl-1,3-dioxolane, and polymers thereof.
U.S. Pat. No. 3,316,216, issued to Fawcett, et al., on Apr. 25, 1967, discloses the preparation of fluorinated dioxolanes of the formula ##STR2## where R, R' and R" can include H, hydrocarbyl, haloalkyl and various other carbon-containing groups, and X and X.sup.1 can include H, halogen and perfluoroalkyl, from fluoroketones and epoxides.
U.S. Pat. No. 3,324,144, issued to Coe, et al., on June 6, 1967, discloses fluorodioxolanes ##STR3## prepared from ketones and epoxides.
U.S. Pat. No. 3,379,736, issued to Dietrich, et al., on Apr. 23, 1968, discloses 4-methylene-1,3-dioxolanes containing either hydrogen and a chlorinated methyl group or a methylene or a chlorinated methylene group in the 2-position.
U.S. Pat. No. 3,450,716, issued to Selman on June 17, 1969, discloses perfluoro-4-oxo-2,5-dimethyl-2-fluorocarbonyl-1,3-dioxolane.
U.S. Pat. No. 3,532,725, issued to Dorfman, et al., on Oct. 6, 1970, discloses the photochlorination of alkyl and aralkyl ester groups of fluorinated esters in the presence of Cl.sub.2, UV radiation and, optionally, CCl.sub.4 as solvent.
U.S. Pat. No. 3,555,100, issued to Garth, et al., on Jan. 12, 1971, discloses the decarbonylation of fluorocarboxylic acid fluorides in the presence of SbF.sub.5.
U.S. Pat. No. 3,557,165, issued to Dorfman, et al., on Jan. 19, 1971, discloses the conversion to acyl halides, in the presence of Lewis acids, of fluorinated esters wherein the ester groups contain polyhalogenated alkyl or aralkyl groups. The disclosed Lewis acids include FeCl.sub.3, SbCl.sub.5, ZnCl.sub.2, ZnCl.sub.4, BF.sub.3, BCl.sub.3, MoCl.sub.5, tin chlorides and metal chlorides, bromides and iodides such as ZrI.sub.4 and antimony bromide.
U.S. Pat. No. 3,749,791, issued to Terrell, et al., on July 31, 1973, discloses halogen-substituted 2,2-bis(trifluoromethyl)-1,3-dioxolanes ##STR4## where X is Cl or F and X' is H, Cl, or F, and their preparation by hydrogenation of 2,2-bis(trifluoromethyl)-1,3-dioxolane.
U.S. Pat. Nos. 3,865,845 and 3,978,030, issued to Resnick on Feb. 11, 1975 and Aug. 31, 1976, respectively, disclose fluorinated dioxoles of the formula ##STR5## where R.sup.1 and R.sup.2 are both perhalogenated hydrocarbyl radicals of 1 to 3 carbon atoms containing at least one F atom and preparation of said dioxoles by reacting the corresponding dioxolanes with Mg. The dioxolanes are prepared by fluorination with SbF.sub.3 -SbCl.sub.4 at 120.degree. C. of 2,2-bis-(perhaloalkyl)-4,4,5,5-tetrachloro-1,3-dioxolanes, which in turn are prepared from haloketones in accordance with the method described in U.S. Pat. No. 2,925,424.
U.S. Pat. No. 4,182,718, issued to Crutchfield, et al., on Jan. 8, 1980, discloses 1,3-dioxolane and 1,3-dioxane polycarbonates and their precursors having the formula: ##STR6## wherein X may be selected from the group consisting of H, CCl.sub.3, CO.sub.2 R, where R is H or lower alkyl, CO.sub.2 M, where M is alkali metal, NH.sub.4 or trialkanolammonium, at least three of the X substituents are other than hydrogen, and n is 1 or 2. The compounds are prepared by the reaction of a halogenated alcohol with a reactive carbonyl to form a halogenated hemi-ketal, followed by reaction with a base to effect cyclization.
U.S. Pat. No. 4,287,124, issued to Siegemund, et al., on Sept. 1, 1981, discloses the preparation of dioxolanes of the formula ##STR7## wherein X and Y, independently, are F or CF.sub.3 and R.sup.1 and R.sup.2 are H or CH.sub.3, by reacting certain acyl halides with a metal fluoride or ammonium fluoride.
U.S. Pat. No. 4,393,227, issued to Squire on July 12, 1983, discloses a process for dechlorinating organic compounds having vicinal chlorine atoms, in particular the preparation of dioxoles from dioxolanes as follows: ##STR8## +MgCl.sub.2, where each of Y and Z independently is H, Cl or F, and each of R.sup.3 and R.sup.4 independently is H, F or trifluoromethyl.
U.S. Pat. No. 4,399,264, issued to Squire on Aug. 16, 1983, discloses perfluoro-1,3-dioxole, homopolymers and copolymers thereof, and a process for making the dioxole.
U.S. Pat. No. 4,431,786, issued to Squire on Feb. 14, 1984, discloses fluorodioxoles of the formula ##STR9## in which Y is hydrogen or chlorine; Z is hydrogen, fluorine, or chlorine; and R is fluorine or the trifluoromethyl group; with the proviso that when R is trifluoromethyl, only one of Y and Z can be hydrogen or chlorine. The patent also discloses polymer and copolymers of these dioxoles.
U.S. Pat. Nos. 4,429,143 and 4,496,750, issued to Anderson, et al., on Jan. 31, 1984 and Jan. 29, 1985, respectively, disclose halogenated dioxolanes of the formula: ##STR10## wherein X.sub.1 is Cl, F, COF, COCl, CO.sub.2 CCl.sub.3, CO.sub.2 R or CO.sub.2 M; R is H or alkyl of 1 to 4 carbon atoms; M is an alkali metal ion or ammonium ion; R.sub.F is a perfluoroalkyl group of 1 to 4 carbon atoms; X.sub.2, X.sub.3, X.sub.4 and X.sub.5, independently are H, Cl or F; with the proviso that when X.sub.2, X.sub.3, X.sub.4 and X.sub.5 are each H, X.sub.1 is CO.sub.2 R or CO.sub.2 M. The patents also discloses perhalogenated dioxoles of the formula: ##STR11## wherein Y.sub.1, Y.sub.2 and Y.sub.3, independently are F or Cl. The patents also disclose homopolymers, copolymers of the dioxoles and methods of making the compounds.
Simmons, et al., Journal of the American Chemical Society 82, 2288 (1960), disclose the preparation of dioxolanes and substituted dioxolanes and specifically mentions that 1,3-dioxolanes were obtained from hexafluoroacetone, sym-difluorotetrachloroacetone and trifluoroacetaldehyde. The general method disclosed for preparing the dioxolanes is the reaction of the appropriate carbonyl compound with an appropriately substituted ethylene halohydrin.